US3919356A - Halogenated norbornene-methanonaphthalene derivatives and their applications - Google Patents
Halogenated norbornene-methanonaphthalene derivatives and their applications Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/02—Halogenated hydrocarbons
- C08K5/03—Halogenated hydrocarbons aromatic, e.g. C6H5-CH2-Cl
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
Definitions
- This invention relates generally to novel compositions of matter which may be generically identified as halogenated norbornene (norbornenyl methanonaphthalene) derivatives.
- Such compositions have been found to have useful properties, particularly as flame retardant additives for normally flammable plastic compositions such as materials containing thermoplastic and thermoset polymers.
- flame retardant additives when blended with the plastic compositions prior to moldings extruding, or the like, are stable at normal processing temperatures and do not discolor the plastic or have an adverse effect on the flow characteristics thereof. Consequently, the use of the subject compositions as flame retardants has solved many of the problems which have heretofore been associated with previously known flame retardants. The latter, in many instances, have been incompatible with certain polymeric compositions and have often downgraded the fabricating capabilities of plastic.
- X is halogen, preferably Cl, Br or F
- Y and Y are each selected from the group consisting of hydrogen, haloger, lower (l-4C) alkyl, lower l-4C) alkoxy, and halogen substituted lower l-4-C) alkyl and alkoxy radicals
- R is selected from the group consisting of hydrogen, lower (l-4C) alkyl, and halogen radicals.
- these products are obtained by a Diels-Alder reaction in which two moles of a halogenated cyclopentadiene are reacted with one mole of a composition having the formula:
- R is selected from the group consisting of hydrogen, lower l-4C) alkyl radicals and halogen radicals.
- Examples of the latter are 4-vinylcyclohexene (a dimer of butadiene), 4-(a-chlorovinyh-l-chlorocyclohexane (a dimer of chloroprene), and d,l-limonene (dipentene, a dimer of isoprene).
- X is bromine, chlorine, or fluorine
- V is bromine, fluorine, chlorine, alkyl or alkoxy radicals
- 2 is a tetravalent cyclic hydrocarbon radical containing at least 5 carbon atoms.
- each example of the reactant forming the Z radical is characterized by dual unsaturation confined to the ring system.
- Applicants class of dienophiles may be regarded as having a divalent cyclic part and a divalent linear part, 4-vinyl-l-cyclohexene being the most important example.
- the novelty and utility of this invention resides in the fact that the subject compositions are prepared by reacting 2 moles of halogenated cyclopentadiene with 1 mole of a diene (e.g., 4-vinyl-l-cyclohexene) that has partly linear unsaturation (e.g., with one vinyl group) and partly cyclic unsaturation (e.g., with one cyclohexene double bond).
- a norbornene methanonaphthalene compound results with a freely rotating central single CC bond.
- compositioni to improve the flame retardant properties of plastics In blending the compositioni to improve the flame retardant properties of plastics, lt has been found that it is only necefllary to use about 1 to 30 per cent by weight of the additive and ordinarily only 5 to 25 per cent by weight. Up to 50 per Gent of additive may be used. As an incidental benefit. these composition! also 3 improve other certain physical properties, i.e., the brittleness is diminished, elasticity is improved, and color holding properties are also enhanced.
- X is halogen
- Y and Y are each selected from the group consisting of hydrogen, halogen, lower (l-4C) alkyl, lower (l-4C) alkoxy, and halogen substituted lower (l-4C) alkoxy and alkyl radicals: and R is selected from the group consisting of hydrogen, lower (l-4C) alkyl, and halogen radicals.
- Another object of the invention is to provide novel methods of preparing compositions described in the previous object.
- EXAMPLE I reflux condenser topped by a Drierite tube.
- two grams of 2,6-ditert-butyl-4'methylphenol was added as an antioxidant.
- the C l-1 was preheated to a refluxing temperature (about l28l30C./76O mm) and 8 moles (2182.4 g.) of C CL, were added dropwise or in a thin stream over a period of 6 hours, gradually increasing the temperature to about 148C, and later to about 160C. afier all of the C -,Cl had been added.
- the temperature was maintained at about 160C. for an additional 7 hours.
- the mixture was then cooled to about l00l40 C.
- the crude product was dissolved in acetone and purified by filtering through charcoal. After concentration of the filtrate, the product, in the form of white crystals, was recovered in a 60 percent yield. Additional small amounts were recovered in the filtrate; and the final filtrate contained a dark brown, viscous tar as the residue.
- Example l the primary difference between Examples l and ll is in the slow addition of C Cl, in Example The rapid exothermic reaction which takes place when the primary reactants are mixed at room temperature, and then heated, increases the risk of a violent, uncontrolled reaction taking place. Moreover, somewhat lower yields (45-60 percent as compared to -82 percent) are obtained by the method set forth in Example ll. Nevertheless, the technique of Example ll can be useful for limited scale experiments.
- EXAMPLE lll Exactly the same reaction set up as Example III was used in this example, but additional amounts of an antioxidant were present in the form of 2 g. of 2,6-di-tertbutyl-4-methylphenol. Also, instead of the acetone, a mixture of methanol and petroleum ether was used to dilute the solidified product before purification. A yield of 1 160.8 g. or 55.3 percent of the theoretical yield was obtained. Combining the washings from the filtration procedures yielded an additional 26.6 percent of the starting material to provide the total yield of 81.9 percent.
- Recrystallization products from the acetone, ethanol, diethyl ether, n-heptane, and/or petroleum ether were dried; and the purified products were all identified as CNB by taking mixed melting points which showed no melting point depression in the various runs. When pure, the crystals consistently melted at 24l243C.
- EXAMPLE lV Ten moles or 1362.3 g. of dipentene or d,1-limonene (C H a colorless liquid, boiling point l78-l80C./760 mm., mol. wt. 136.23, were mixed at room temperature with 16 moles (4365 g.) of hexachlorocyclopentadiene. Five grams of 2,6-di-tert-butyl- 4-methylphenol (antioxidant) and 7 g. of dibutyltin dimaleate (scavenger) were added to this mixture.
- the product was identified as 6-(1, 4 ,5 ,6 ,7 ,7 -hexachloro-2 -methyl:5 -porbornen-Z y1)-l ,4, 4a,5 ,6,7,8,8a-octahydro-1,2,3 ,4,9,9-hexachloro-8a-methyl-1,4-methanonaphthalene, a compound having the following structure:
- EXAMPLE v The following equation represents the synthesis of another Diels-Alder adduct, 6-(1 ,4 ,5 ,6'-tetrachloro- 7 ,7 -dimethoxy-5'-norbornen-2 '-yl) 1 ,2,3 ,4-tetrachloro-9,9-dimethoxy-1 ,4,4a,5,6,7,8,8a-octahydro- 1,4-methan0naphthalene, C221-l 4ClaO4, or tetramethoxy chlorinated norbornene derivative (hereinafter TCNB):
- Hexabromocyclopentadiene or C Br (a yellow, crystalline solid, mp. 8385C.), 0.1 mole or 53.95 g., was mixed at room temperature with 0.05 mole or 5.4 g. ol 4-vinyl-l-cyclohexene (a colorless liquid, b.p. l30C./760mm. Upon heating to 50C., a yellow, homogeneous solution was formed. It was heated for 3 hours at lO-l30C. and for 4.5 hours at l30l35C. The brown product was treated with boiling acetone and then with boiling tetrachloroethylene.
- the mixture was heated in a nitrogen atmosphere, with mechanical stirring, to l40l63C for 5 hours and to l65C for 6 hours.
- the liquid by-products of the reaction were removed by distillation at a reduced pressure.
- the residue of the distillation solid ified to a clear, glassy, dark brown solid which was purified by recrystallization first from acetone and then from ether, filtering in the presence of active charcoal for decolorization of the solutions.
- the purified solid product formed white crystals
- the residue of the distillation after cooling was a dark brown solid.
- the compound was purified by repeated crystallization first from the chloroform and then from isopropyl alcohol and acetone, using acti ve charcoal for decolorizag'on o f tl e solutions.
- the final crystallization yielded a ⁇ Thite solid, mp. 6275C, which after drying in a vacuum oven at room temperature was identified as PHNB or C H Cl by analyses of carbon, hydrogen, and chlorine, and by a molecular weight determination. as follows:
- the melting point range is explained by the presence 130 to 160C for hours small of several geometrical isomers in the endoor exopo- 5 grams) of unreacted raw F P and of volanls sifions of the two groups in the norbomene products were removed by distillation at up to 70 C of and in the methanonaphthalene rings, as we” as due to vapor temperature and 0.09 mm Hg. pressure.
- the f 'e spectrum showed absorption bands black for discoloration.
- THNB THNB
- 5962C calwas prepared from 7 parts by weight of DENB, 50 parts culated molecular weight, 203.88), was mixed at room of polyvinylchloride, 20 parts of the Marbon acrylonitemperature with 0.086 mole or 9.3 grams of 4-vinyl-ltrile-butadiene-styrene graft polymer resin, 2 parts of cyclohexene or C H and 0.13 gram of 2,6-di-tert.- the plasticizer, 2 parts of the stabilizer, 0.5 parts of antibutyl-4-methylphenol.
- the mixture was heated with oxidant, 0.5 parts of the lubricant and 0.5 parts of the stirring in nitrogen atmosphere, at a gradually increassynergistic fire retardant, antimony (111) oxide. This ing temperature, for 1 1.5 hours at 130 to 180C. Volamixture was milled at 320F for 4 minutes and comtile by-products were distilled from the crude reaction pression-molded at 340F and 50,000 psi for 2 minutes. product at up to 121C of vapor temperature and at 0.1 The resulting plastic sheet was pale yellowish-white and mm Hg pressure.
- the desired intermediate distilled at l24-l42C/ 1 mm. It was purified by another distillation at l32l35C/l mm and identified as l,l-di-nbutoxy-2,3,4,S-tetrachlorocyclopenta-Z,4-diene by elementary analyses, the infrared spectrum, and a determination of the molecular weight.
- CICH,CH O hexachlorocyclopentadiene
- EXAMPLE XllI Chloroprene dimer, 4-(B-chlorovinyl)-l-chloro-lcyclohexene (hereinafter referred to as CD), was prepared in the manner of Klebamkif et al., VysokomlekuLSoedin, 4, 1 145-50 (1962). [See also Chem. Abstracts 59, 1819a (1963)]. A 177.0 g. portion of the CD so prepared was charged to a reaction vessel and heated under nitrogen to 70C. Over a period of four hours, 545.0 g. of hexachlorocyclopentadiene was added to the reaction vessel with stirring as the temperature was gradually raised to 160C.
- CD 4-(B-chlorovinyl)-l-chloro-lcyclohexene
- a compound of the same empirical formula O l-1 C1 was obtained by chlorination of the product of Example l (CNB) in carbon tetrachloride solution at about 60C in the presence of UV light.
- the CNB in Examples 1 through III was prepared by premixing hexachlorocyclopentadiene and 4-vinyl-1- cyclohexene as well as by the addition of C Cl to preheated 4-vinyl-l-cyclohexene.
- Examples xiv and xv set forth hereinbelow illustrate that CNB may be prepared by the gradual addition of 4-vinyl-l-cyclohexene to preheated C Cl,,-, i.e., it can be prepared by the reverse addition of reactants.
- the second 14 half of the 4-vinyl-1-cyclohexene was added over a period of 40 minutes with continuous heating and stirring under a nitrogen atmosphere. The heating and stirring was continued for an additional 9 hours and 23 minutes at an average temperature of 183 C. The total time of addition and heating was 11 hours.
- the mixture was cooled to 138 C. and precipitated by pouring into 900 parts by weight of technical grade isopropyl alcohol.
- the principal product was CNB which was precipitated in the form of off-white crystals.
- the mixture was cooled to room temperature and CNB was collected by filtration. After drying over calcium sulfate at a reduced pressure in a vacuum oven, the yield of CNB was 991.2 parts by weight or 82 percent.
- CNB may be improved to 82 percent by the reverse addition procedure, i.e., addition of a 4-viny1-1-cyclohexene to preheated C C1
- CNB was synthesized using a 2:1 molar ratio of C Cl to 4-vinyLl-cyclohexene.
- a higher yield of CNB was obtained by employing an excess of C Cl in the reaction mixture throughout the reaction.
- the molar ratio of C Cl to 4- vinyl-1-cyclohexene was 3:1 or 50 percent excess over the calculated amount of C C1 capable of reacting with the 4-vin yl- 1 -cyclohexene.
- the reaction proceeded as follows. 900.3 parts by weight technical grade hexachlorocyclopentadiene (C Cl was placed in a reaction vessel. 2.04 parts by weight of 2,6-di-tert-butyl-4-methylpheno1 was added as an antioxidant and an inhibitor for free radical polymerization. The mixture was heated to 160 C. under a nitrogen atmosphere and a yellowish orange solution was formed. 119.0 parts by weight of pure 4-vinyl-lcyclohexene was added to the solution over a period of 2% hours at 160 C. The temperature was retained in the mixture with stirring over a period of 12 hours.
- C Cl technical grade hexachlorocyclopentadiene
- Burning Tests for Plastics Underwriters Laboratories Subject 94 (U.L. Test). All tests qualified as Self-Extinguishing, Group 1 in that they did not drip any flaming materials or droplets during burning test.
- ABS resin is ucrylonitrile-butadiene-styrene graft copolymer.
- the product retained the high tensile strength, hardness, and heat distortion temperature as ABS resins. It had also a high flexural strength and was not brittle.
- the flow of the resin was improved significantly by the presence of CNB, in contrast to other flame retardants known in the art which retard the flow of hot plastics so that full bars and plaques cannot be produced in the above given temperature range for milling and molding whereas in a higher temperature range a decomposition sets in. Because of its high thermal stability, lack of decomposition, and improved flow, as well as the effective flame retardance, CNB showed surprisingly excellent results and outclassed in its performance in plastics the other additives known in the art.
- the novel composition of ABS resins containing CNB was classified as belonging to group l, Self-extinguishing; group I is the best plastic, i.e., it is self-extinguishing, and the sample does not drip in contact with flame. Time of self-extinguishing of the flame (average for 6 ignitions for 60 mil thin samples) was only 2.8 seconds, and the minimum/- maximum ratios of the tests (in seconds) was one-fifth.
- EXAMPLE XVII A relatively pure sample of CNB, prepared in accordance with Example I, was rated for its flame retardant properties in a large class of polymeric materials. Unless otherwise noted, the CNB was milled into the polymeric resin to obtain a homogeneous blend. Each sample contained CNB in the amount of 16.5 percent by weight, and except for the samples which were not millable, also included 7.7% by wieght of Sb O a conven- 17 tional stabilizer that is synergistic to flame retardance to the halogen compounds of this invention.
- CNB acts not only as a fire retardant, but also improves the hot flow of resins listed in 18 rene) and acrylonitrile (or substituted acrylonitrile) in the presence of the prepolymerized polybutadiene substrate.
- An acrylate ester may also be used in addition to styrene and acrylonitrile or in place of acrylonitrile Polybutadiene, linear Polybutadiene, crosslinked Butyl rubber (polyisobutylene) Polyamide (nylon) Polyamide (nylon, Type 8) Poly( styreneacrylonitrile Polystyrene Ethylene-propylene rubber Ethylene-propylene terpolymer Polyethylene Poly(cyclopentadiene) Methyl methacrylate/ a-chloroacrylonitrile 80:20 copolymer Styrene/a-chloroacrylonitrile 75:25 copoiymer Styrene/achloroacrylonitrile/ methyl methacry late 60: 10:30 copolymer Vinyl toluene/ butadiene 9H) copolymer Acrylic rubber Polycarbonate Polypropylene Styrene/butadiene Division Firestone HD-55-A, 35% cis
- ABS graft polymers may also be prepared tures.
- CNB and its lower-melting geometriusing other rubbery substrates including diene copolycal isomers of the same empirical formula C l-l Cl mers and elastomers made from monomers other than designated as INB (see Examples XIV and XV) act as dienes, such as polyisobutylene, ethylene-propylene mold release agents so that the use of flammable mold copolymers, ethylene-vinyl acetate copolymers, acrylrelease agents (such as Pluronic F-38, known in the 10 ates, for example, polybutylacrylate and the like.
- dienes such as polyisobutylene, ethylene-propylene mold release agents so that the use of flammable mold copolymers, ethylene-vinyl acetate copolymers, acrylrelease agents (such as Pluronic F-38, known in the 10 ates, for example, polybutylacrylate and the like.
- Chloart is not required for ABS and ABS-type resins, when rinated polyethylene and olefin oxide rubbers are also at least l3% of INB is employed in the resin composielastomers that may be used as substrates in the prepations.
- the CNB and its isomers also diminish brittleness ration of graft polymers.
- ABS-type polymers are also and improve on the flexibility of polymeric composimade by milling together (or otherwise thoroughly mixtions.
- EXAMPLE XVIII The compound identified as TCNB, made in accorand not dance with Example V, was tested as a flame retardant l5 additive. It was mixed with certain acrylonitrile-butadiene-styrene resins at room temperature, in powdery form, and some additives were also added as follows:
- TCNB (as well as of CNB, see above, and other products of this invention) was the fact that they did not show any tendency to sublime at the conditions of milling and molding, i.e., at elevated temperatures, whereas numerous other flame retardant additives known in the art (and not related in their structure and properties to the products of this invention) did show the tendency to sublime from the hot resin, which was found to be inconvenient and sometimes hazardous for the operator. This difference is significant in favor of practical use of the products of this invention, including CNB and TCNB.
- TCNB or C H CI O was blended at the level of l52 percent by weight (with 4-7 percent by weight of antimony (Ill) oxide present) with other resins (listed in more detail previously from the use of CNB in various resins), including polystyrene; poly-(styrene-acrylonitrile) or polySAN; polypropylene; and Bisphenol-A polycarbonate and in this manner self-extinguishing and flame retardant resin compositions were obtained, with improved flow of the resins and other attractive physical properties.
- other resins listed in more detail previously from the use of CNB in various resins
- C H Br was found to have a similar flame retardant effect in polySAN, polystyrene, polypropylene, and in other plastics at comparable levels of concentration.
- EXAMPLE XX The product identified as BCN, made in accordance with Example Xll, was also found to be an effective flame retardant in various resins. About 15-22 percent of the flame retardant was used in resins along with about 4-7 percent of antimony (III) oxide in order to prepare non-buming or immediately self-extinguishing samples of plastics, according to the Underwriters Laboratories vertical test (Class I). Similar resins were fireproofed with this new compound as those described in Example XVll.
- CNB may be used with compositions that are normally considered flame-resistant and improve the properties of 21 these compositions as well.
- the principal advantage of using CNB with compositions that are normally flameretardant such as chlorinated natural rubber is that it improves upon the flow characteristics of the polymeric material, its ease of molding and milling, tends to diminish the brittleness of the compounded resins and makes them completely non-flammable.
- CNB vertical flammability
- Sb O 22 percent by weight of Sb O a conventional stabilizer and flame-retardant.
- l3.2 percent of CNB and 7.7 percent of Sb O were used.
- the characteristic properties of the polymeric materials such as brittleness, flow, flexibility, etc. are as follows.
- the flammability rate was as follows.
- BRN Burns readily, non self-extinguishing FR Fire retardant, burns for specified seconds after removal of flame.
- the physical properties of the fire retardant compositions Vlll of Table lll(b) should be compared to that of composition 11 of Table lll( a) as a control without a fire retardant additive.
- the properties of composition IX of Table lll(b) should be compared with that of composition ll] of Table lll(a) as a control without the tire retardant additive. This comparison will show that the desirable properties of the flexible polyvinyl chloride- (acrylonitrilebutadiene-styrene) graft polymer sheet are retained while the additional advantage of considerably increased tensile strength and tear strength is accomplished through addition of [NE as set forth in Examples Xlll and XIV.
- Desirable variations of physical properties of the polyvinyl chloride-graft polymer (ABS) resins, either with or without plasticizers, can be obtained by varying the proportion of CNB or other additives, (i.e., halogenated norbomene-methanonaphthalene type) of this invention.
- CNB or other additives i.e., halogenated norbomene-methanonaphthalene type
- CNB land [NB are also useful in thermoplastic and thermoset materials that must be utilized as containers for edible compositions due to their essentially nontoxic characteristics. Experimental tests with rats and rabbits found the toxicity level to be extremely low (LD-SO of more than 10 g. ofCNB per l kg. of body weight with no deaths observed. The contact was tested both on the skin and orally). The non-toxic aspects of the additives makes them exceptionally useful as fire retardants and reduces the danger to operators working 26 cured elastomers, thermosets, bituminous compositions, paints, lacquers, etc.
- the CNB, [N8 and other halogenated norbor- .nenemethano-naphthalene derivatives are illustrated herein as additives to given thermoplastic compositions.
- the additives may be used with a wide variety of plastic materials with properties ranging from elastomeric to hard, brittle, resinous polymers.
- the additives may be blended with halogenated resins,
- red- BRN NF Both "A” and B” are inlinked polyclear, light brown solid drips completely crosslinked amide (Nylon red-brown type) film Thermoset Pale yellow Pale yellow- SE, 3 sec. NF Reduced brittleness and phenol-formbrown. glossy tan, glossy increased non-flammability aldehyde resin solid solid for 5" (with CNB).
- Polyurea, a Yellowish- Yellow SE, 7.2 sec. SE immediately, Advantages for 5" include crosslinked white white solid. black smoke no smoke immediate self-extinguishresin smooth suring character and improved face smoothness of surface texture.
- thermoset Yellow, Yellow, in 8 without impairing casting from glossy glossy Barcol hardness a.o. promaleale-iso solid solid perties. 5" much less phthalate polybrittle. ester and styrene crosslinked Pale, Pale, BRN SE, 4.7 sec. Non-flammability achieved thermoset cast- Yellow, Yellow, in 8" without impairing ing from fumaglossy glossy physical properties. 8" rate-isophthasolid solid much less brittle, late polyester and styrene Rigid poly- Off-white White, BRN SE, l 1 sec. Fire retardance achieved urethane foam, rigid rigid, (quickly and in "B” without any signia crosslinked foam foam completely) ficant change. Some imresin provement in color and hardness in 8".
- Tables 1-1 set forth blends of CNB with thermoplastic resins and illustrate the use of CNB as a fire retardant additive. It will be understood from Table N that CNB may be blended with therr'noset (crosslinked) resins as well as with normally fire retardant compositions, both in the therrnoset and thermoplastic category. When blended with the therrnoset resins, a thermoset fire retardant composition is obtained. Preferably, the blending is performed before the composition is crosslinked, however, CNB may be mixed with a previously crosslinked material, such as for example, crosslinked polybutadiene and utilized thereafter. When the CNB TABLE VI Fire Retardance Elongation Values Resin Blended Control (The with CNB (16.5
- Resin Curing System Resin Alone wtfl) & Molded Blended Temp. Time with Same Curwith Same Cur- Base Resin Control With CNB Agent F (Minutes) ing Agents ing Agents Butyl Rubber BRN FR. 0.15 2% Sulfur 320 20 563 683 No. 13247-E 4 in/ in/min.
- Neoprene WRT SE l NF 5% ZnO 320 20 650 692 sec.
- MgO Styrene-Buta- BRN SE immed- 2% Sulfur 340 20 433 542 diene Rubber iately (SBR No. 10726)
- Ethylene- BRN NF [3% Sulfur 320 20 442 $33
- Propylene terpolymer (EPT No. l9694-Cll) Chlorinated SE, 2 NF ⁇ 5% ZnO 320 20 I3 400 Polyethylene sec.
- the norbornenemethanonaphthalene compounds are capable of being used as fire retardant additives in a variety of thermoplastic compositions. It will also be understood that superior to that of the thermoplastic compositions set forth above. Examples of the use of substituted norbornene-methanonaphthalene compounds in paints and coatings are set forth in Table VII herein below.
- thermoplastic compositions may be incorporated in paints, coatings and bituminous coinpositions and also that the norbomene-methanonaphthalene compounds may be incorporated in paints, coatings and bituminous compositions without utilizing the thermoplastic as a carrier.
- fire retardant additives may be used in paints, coatings, etc., as additives along with the inert additive fillers such as titanium dioxide, diatomaceous earth, zinc oxide, etc.
- the resulting coatings and paints will thus exhibit fire retardant characteristics equal to or no drip, slight smoke While this invention has been described in connection with certain specific embodiments thereof, it is to be understood that this is by way of illustration and not by way of limitation; and the scope of the appended claims should be construed as broadly as the prior art will permit.
- a flame retardant composition comprising (A) a polymeric base consisting of at least one polymer selected from the group consisting of polyisoprene, acrylinitrile-butadiene-styrene graft polymer and other ABS type resins, linear polybutadiene, crosslinked polybutandiene, polyisobutylene, polyamide, poly( styrene-acrylonitrile), polystyrene, polyvinyl chloride, ethylene-propylene rubber, ethylene-propylene terpolymer, polyethylene, poly(cyclopentadiene), acrylic rubber, polyphenylene oxide, polycarbonate, polyurethane, polypropylene and high impact polystyrene (B) a flame-retarding amount of an additive of the struc ture lected from the group consisting of antimony, oxide, zinc borate and mixtures thereof.
- the flame-retardant polymeric composition comprising (A) a polymeric base consisting of from about 5% to about 95% by weight polyvinylchloride and correspondingly from about 95% to about 5% by weight of an acrylonitrilebutadiene-styrene graft polymer, and (B) a flame-retarding amount of an additive of the structure C1 Cl 3.
- a flame retardant polymeric composition comprising (A) a polymeric base consisting of at least one thermoset resin selected from the group consisting of epoxy resins, phenolformaldehyde resins, thermoset polyester resins, thermoset polyurea resins and (B) a flameretarding amount of an additive of the structure 4.
- a flame retardant polymeric composition comprising (A) a polymeric base selected from the group consisting of chlorinated natural rubber, chlorinated polyethylene, chlorinated polypropylene, chlorinated ethylene-propylene polymer and polychloroprene and (B) a flame-retarding amount of an additive of the structure F C1 C1 5.
Abstract
WHEREIN X is halogen and Y and Y'' are independently selected from the group consisting of hydrogen, halogen, lower alkyl and C1 to C4 alkoxy, and a synergistic additive selected from the group consisting of antimony oxide and zinc borate. In addition to flame-retardant characteristics, these polymeric compositions exhibit improved melt flow and thermal processability.
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2706827A1 (en) * | 1976-02-20 | 1977-09-01 | Ici Ltd | REINFORCED POLYAMIDE COMPOUND |
US4056508A (en) * | 1973-10-27 | 1977-11-01 | Dynamit Nobel Aktiengesellschaft | Difficultly inflammable polyester molding compositions |
DE2656883A1 (en) * | 1975-08-27 | 1978-06-22 | Rhone Poulenc Ind | FIRE-RESISTANT POLYAMIDE COMPOSITIONS |
EP0085834A1 (en) * | 1982-01-25 | 1983-08-17 | General Electric Company | Colour inhibiting flame-retardant consisting of a stable halogenated organic compound and a boron compound |
WO1987001713A1 (en) | 1985-09-17 | 1987-03-26 | Pennwalt Corporation | Tetrahalophthalate esters as flame retardants for polyphenylene ether resins |
US4684672A (en) * | 1983-01-10 | 1987-08-04 | Buchanan Robert L | Novel rubber connectors and other rubber parts for use in human infusion sets and rubber |
US4904795A (en) * | 1988-03-25 | 1990-02-27 | Pennwalt Corporation | Halogen substituted phthalimide flame retardants |
EP0364729A1 (en) * | 1988-10-12 | 1990-04-25 | General Electric Company | Polymer-based material which comprises a flame-retardant and optionally a plasticizer and further conventionally used additives |
US4927873A (en) * | 1988-03-25 | 1990-05-22 | Pennwalt Corporation | Halophenyl ester flame retardants for polyphenylene ether resins |
US4999391A (en) * | 1988-03-25 | 1991-03-12 | Atochem North America, Inc. | Halogen substituted phthalimide flame retardants |
US5043374A (en) * | 1988-03-25 | 1991-08-27 | Atochem North America, Inc. | Halogenated polyester flame retardants for polyphenylene ether, polyolefin and polyethylene terephthalate resins |
WO1997033848A1 (en) * | 1996-03-13 | 1997-09-18 | Optatech Corporation | Method for preparing norbornene and substituted derivatives of norbornene |
EP1164158A1 (en) * | 1999-10-27 | 2001-12-19 | Kaneka Corporation | Extruded styrene resin foam and process for producing the same |
US6338230B1 (en) | 1999-10-25 | 2002-01-15 | Davey John F | Simulated shake shingle |
EP1557456A1 (en) * | 2002-10-29 | 2005-07-27 | Dai-Ichi Kogyo Seiyaku Co., Ltd. | Flame retardant for plastic |
US20050249918A1 (en) * | 2004-05-07 | 2005-11-10 | Building Materials Investment Corporation | Shingle and mat tensile strength with urea formaldehyde resin modifier |
US20070149661A1 (en) * | 2005-12-23 | 2007-06-28 | Sanjay Gurbasappa Charati | Polycarbonate composition, method of manufacture thereof and articles comprising the same |
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Publication number | Priority date | Publication date | Assignee | Title |
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US4056508A (en) * | 1973-10-27 | 1977-11-01 | Dynamit Nobel Aktiengesellschaft | Difficultly inflammable polyester molding compositions |
DE2656883A1 (en) * | 1975-08-27 | 1978-06-22 | Rhone Poulenc Ind | FIRE-RESISTANT POLYAMIDE COMPOSITIONS |
DE2706827C2 (en) * | 1976-02-20 | 1987-03-19 | Imperial Chemical Industries Ltd., London, Gb | |
DE2706827A1 (en) * | 1976-02-20 | 1977-09-01 | Ici Ltd | REINFORCED POLYAMIDE COMPOUND |
EP0085834A1 (en) * | 1982-01-25 | 1983-08-17 | General Electric Company | Colour inhibiting flame-retardant consisting of a stable halogenated organic compound and a boron compound |
US4684672A (en) * | 1983-01-10 | 1987-08-04 | Buchanan Robert L | Novel rubber connectors and other rubber parts for use in human infusion sets and rubber |
WO1987001713A1 (en) | 1985-09-17 | 1987-03-26 | Pennwalt Corporation | Tetrahalophthalate esters as flame retardants for polyphenylene ether resins |
US5043374A (en) * | 1988-03-25 | 1991-08-27 | Atochem North America, Inc. | Halogenated polyester flame retardants for polyphenylene ether, polyolefin and polyethylene terephthalate resins |
US4904795A (en) * | 1988-03-25 | 1990-02-27 | Pennwalt Corporation | Halogen substituted phthalimide flame retardants |
US4927873A (en) * | 1988-03-25 | 1990-05-22 | Pennwalt Corporation | Halophenyl ester flame retardants for polyphenylene ether resins |
US4999391A (en) * | 1988-03-25 | 1991-03-12 | Atochem North America, Inc. | Halogen substituted phthalimide flame retardants |
US5182325A (en) * | 1988-10-12 | 1993-01-26 | General Electric Co. | Polymer containing fluorinated polymer and boron compound |
EP0364729A1 (en) * | 1988-10-12 | 1990-04-25 | General Electric Company | Polymer-based material which comprises a flame-retardant and optionally a plasticizer and further conventionally used additives |
KR100545067B1 (en) * | 1996-03-13 | 2006-09-13 | (주)폴리머스넷 | Method for preparing norbornene and substituted norbornene derivatives |
WO1997033848A1 (en) * | 1996-03-13 | 1997-09-18 | Optatech Corporation | Method for preparing norbornene and substituted derivatives of norbornene |
US6294706B1 (en) * | 1996-03-13 | 2001-09-25 | Opatatech Corporation | Method for preparing norbornene and substituted derivatives of norbornene |
CN1083821C (en) * | 1996-03-13 | 2002-05-01 | 奥普塔技术公司 | Method for preparing norbornene and substituted derivatives of norbornene |
US6338230B1 (en) | 1999-10-25 | 2002-01-15 | Davey John F | Simulated shake shingle |
EP1164158A1 (en) * | 1999-10-27 | 2001-12-19 | Kaneka Corporation | Extruded styrene resin foam and process for producing the same |
EP1164158A4 (en) * | 1999-10-27 | 2004-04-07 | Kaneka Corp | Extruded styrene resin foam and process for producing the same |
EP1557456A1 (en) * | 2002-10-29 | 2005-07-27 | Dai-Ichi Kogyo Seiyaku Co., Ltd. | Flame retardant for plastic |
EP1557456A4 (en) * | 2002-10-29 | 2010-07-07 | Dai Ichi Kogyo Seiyaku Co Ltd | Flame retardant for plastic |
US20050249918A1 (en) * | 2004-05-07 | 2005-11-10 | Building Materials Investment Corporation | Shingle and mat tensile strength with urea formaldehyde resin modifier |
US7272915B2 (en) | 2004-05-07 | 2007-09-25 | Building Materials Investment Corporation | Shingle and mat tensile strength with urea formaldehyde resin modifier |
US20070149661A1 (en) * | 2005-12-23 | 2007-06-28 | Sanjay Gurbasappa Charati | Polycarbonate composition, method of manufacture thereof and articles comprising the same |
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